Perfluoroalkyl-thioether alcohols, esters and polymers thereof

ABSTRACT

Perfluoroalkyl group containing thioether alcohols are converted into Alpha , Beta -Unsaturated mono-, di- and triesters from which polymers are derived having soil repellent properties particularly if applied to substrates such as textiles, paper and leather.

United States Patent [191 Kleiner et al.

PERFLUOROALKYL-Tl-llOETl-IER ALCOHOLS, ESTERS AND POLYMERS THEREOF Inventors: Edward Karl Kleiner, New York;

Martin Knell, Ossining, both of NY.

Assignee: Ciba-Geigy Corporation, Ardsley,

Filed: Apr. 30, 1973 Appl. No.: 355,640

Related U.S. Application Data U.S. Cl 260/609 R; 8/1 15.6; 8/116 R; 260/486 R Int. Cl. C07c 149/18 [451 May 20, 1975 [58] Field of Search 260/609 R [56] References Cited UNITED STATES PATENTS 3,786,089 I/l974 Rondestvedt 260/609 R FOREIGN PATENTS OR APPLICATIONS 1,594,925 8/1969 Germany 260/609 R Primary Examiner-Elbert L. Roberts Assistant Examiner-D. R. Phillips Attorney, Agent, or Firm-Edward McC. Roberts; Joseph G. Kolodny; Prabodh l. Almaula [5 7 ABSTRACT Perfluoroalkyl group containing thioether alcohols are converted into a,B-Unsaturated mono-, diand triesters from which polymers are derived having soil repellent properties particularly if applied to substrates such as textiles, paper and leather.

8 Claims, No Drawings 1 2 PERFLUOROALKYL-THIOETHER ALCOHOLS, Type Ester R R R ESTERS AND POLYMERS THEREOF Aerylate H H H Methacrylate -H H CI-I,1 Fumarate -H AR, H RELATED APPLICATION M m AR, -H H 5 Mcsaconatc H -AR, -C H, This application IS a division of application Ser. No. Citraconate -AR, -H -CH:, 299,487, filed Oct. 20, 1972, now us. Pat. No. I 3,763,l I 16, which is a continuation-in-part of applica- Methylene malonmc tion Ser. No. 199,793, filed Nov. 17, 1971, now aban- CiS-ACOHiIflIC 1 i r doned, which is a continuation-in-part of application Ser. No. 720,370, filed Apr. 10, 1968, now pending. mm Mme H SUMMARY OF THE INVENTION Note that the acrylate and methacrylate type esters This invention relates to improve soil repellent finare within the Scope of this invention only when Rfis ishes which are based on their property of possessing l5 CPFZPJFIOCQF'ZQ low free surface energy. The polymers derived from the If monomers of type H are homo or copolymerizedi disclosed compounds provide oil and water repellent Polymers are Obtained Containing the following p finishes useful to treat materials such as textiles, paper, "8 units or moieties leather, painted wood and metallic surfaces and the like.

More specifically this disclosure relates to novel thioether alcohols which can be converted into afi-unsatuf rated mono-, diand triesters. Polymers derived from these esters are highly desirable in application as surface finishes to provide a desirable degree of low free surface energy.

The thioether alcohols of this invention contain a perfluoroalkyl group and are of the formula:

I RJCMHWSCHHHOH wherein R A, R R R are as defined above. wherein M is 2 to 12; DETAILED DESCRIPTION OF THE INVENTION 1 12; PERFLUOROALKYLTHIOETHER ALCOHOLS R; IS C F OC F P i 3 to 13, d f bl 6 to 12; Several alternative techniques exist for the synthesis and q is 2 to 8. 0f the perfluoroalkylthioether alcohols of the present In formula I, a most desirable class of alcohols is invention and are of the generic Structure: where p is 6 to 12, m is 2 and n is (CH to e. I R,C,,.H ,,,sC,,H ,,oH

Compounds not within the scope of the present in- A suitable method for forming this alcohol is by revention but useful in preparing compounds of formula duction of esters or acids of types IV and V employing II described below are compounds of formula I wherein conventional reducing agents such as lithium aluminum R, is C F and p is as herein before defined. hydride, diisobutyl aluminum hydride, hydrogen and The novel monomers derived from the R -thioether metal catalysts:

reduction R C H SC H OH I m 2m n 2n V R C H SC H COOH alcohols of type I are, -unsaturated esters having the Employing this route of synthesis, the desired R thiofollowing structure II: ether alcohols of type Ia are obtained where n is equal 1 or larger than 3, as shown by the following example: ll R A /R Rpmu n scu cmcoocu wetmc u s mcu cu ou C=C The synthesis of esters and acids of types IV and V 3 2 is disclosed in US. Pat. No. 3,172,910 and they are prepared by the addition of R -mercaptans of type VI wherein to unsaturated ethers (or acids) of type VII:

a. R and R are hydrogen and R is hydrogen or if -"5 "-r zm n 0 methyl when R, to C,,F OCq F- q; or T W v b. R, R R are hydrogen, methyl, R A- or R;ACH

with the proviso that at least one or two of the R If n e ters of acids Of type VII the alkylene linkage substituents represent R A- or, RjACH If R, R is zero, as this is the case for acrylic esters or acrylic represent th g substitucnts as defined b f acid, then esters or acids of types War or Va are obmula II represents the following esters: m e

Reduction of esters or acids of type IVa and Va yield R thioether alcohols of type Ia, where n is 3, the smallest possible n-number that can be obtained employing the outlined route of synthesis:

Another general technique for formation of the thioether alcohol of type I is by a free radical addition of R mercaptans oftype VI and unsaturated alcohols of type VIII and preferably a terminally unsaturated alcohol of type VIIIa:

The free radical catalyzed addition may be undertaken in accordance with the general procedures described in US. Pat. No. 3,172,910.

Of special interest are lower, terminally unsaturated alcohols of type VIIIa such as allyl alcohol yielding R,- thioether alcohols of type la,

VI vinyl acetate IX The R acetate IX can easily be hydrolized to yield R thioether alcohols of type Ib, where n is 2:

It is, of course, understood that the R thioether alcohols of type I, where n is greater than 2 can also be prepared employing esters of types X and Xa instead of the corresponding alcohols of types VIII and VIIIa for the addition reaction with R mercaptans:

Hydrolysis of IXa yields R thioether alcohols of type I, as shown above.

A technique for formation of a thioether alcohol disclosed as an intermediate compound and of the formula C F C I-I SC H.,Ol-I has been shown in Blochl, West German Patent 1,594,925 involving reaction of ethylene oxide with a mercaptan of the formula C F C I-I SI-I.

R, mercaptans of the formula Rp n su have been disclosed as suitable in formation of the novel perfluoroalkyl thioether alcohols. These mercaptans are described in a number of US. patents and other literature publications including US. Pat. Nos. 2,894,991; 2,961,470; 2,965,677; 3,088,849; 3,172,910; and 3,544,663.

A most convenient synthesis method was found to be a thiourea method according to the following equation:

Xl VI The R, groups as previously defined are of the formula C F or C F OC F wherein p is 3 to 18 and preferably 6 to 12 and q is 2 to 8. The perfluoroalkyl constituents may be branched or straight chains. The perfluoroalkyl thioether alcohols where R, is C,,F are not within the scope of the present invention but are useful in preparing the esters of the present invention hereinbefore described as structure II.

The alkylene linkage groups in Formula I, C,,,l-l and C l-I have been previously defined wherein m is 2 to 12 and n is 2 to 12 respectively. As disclosed by the techniques of synthesis, both C,,,l-I and C l-l may be branched or linear. From the standpoing of commercial use, it is considered desirable that C I-I as well as C,,,H are linear. Additionally over the disclosed range of m and n, the respective values may be different or identical.

R, Tl-IlOETI-IER MONOMERS OF FORMULA II The monomers derived from the perfluoroalkyl thioether alcohols discussed previously are of the formula:

wherein R A- is Rp u,,,sc,ii,,ocas defined above and a. R and R are hydrogen and R is hydrogen or methyl when R, is C F OC F or b. R, R R are hydrogen, methyl R,A- or R,ACH

with the proviso that at least one or two of the R- substituents represent RfA' or R,ACI-I These compounds may be prepared following procedures familiar to those skilled in the art. With the exception of the perfluoroalkyl thioether alcohols, the starting materials are generally commercially available and/or may be prepared in accordance with well known techniques.

The ester monomers of Formula II are obtained from the perfluoroalkyl thioether alcohols and acrylic, methacrylic, fumaric, maleic, mesaconic, citraconic itaconic methylene malonic or aconitic acids, and acid chlorides or acid anhydrides if obtainable and esters of these acids by well known esterification or transesterification techniques.

Since many of the starting acids have high melting points or poor solubility characteristics, it is usually preferable to employ the acid chlorides, anhydrides or lower alkyl esters of the listed acids.

Instead of employing the perfluoroalkyl thioether as a reactant material, it is also possible and often advan- 2 +=tcHcoo H I ons 2 m +=CHCOOH3)2, truns- (CHCOCIC Fl POLYMERIZATION OF PERFLUOROALKYL THIOETHER MONOMERS Polymers possessing soil repellent properties may be formed from R; thioether monomers of Formula II,

wherein R A, R, R and R have been previously defined.

Both homoand copolymers may be formed utilizing the formula II reactant to form a constituent of the polymer chain. The polymers contemplated by this invention include, homopolymers, copolymers with other ethylenically unsaturated monomers, and physical blends of such homopolymers and copolymers together and/or with other polymers.

The polymers and copolymers derived from the thioether monomers will have units in the polymeric chain of the formula:

III

The formula I] R,thioether monomers and polymers derived therefrom can be considered to be divided into two distinct classes due to their polymerization behavior. This separate distinction is based on the structure characteristics based on the numbers of R, group per monomeric moiety in the polymer chain. These two classes are based on polymers derived from acrylates and methacrylates on one hand, as opposed to fuma- 0 .1 0 (CH3) cooc n sc SC H P Ci] COOC l" C if n m 21:23 2 n zn m rates, maleates, mesaconates, citraconates, itaconates, methylene malonates, and aconitates on the other hand. Polymers derived from acrylates and methacrylates are within the scope of this invention only when the R; substituent on the monomer is C F QC F Turning to the first class which are acrylates and t a Mr '1 l R L trans 1- 20 1. 0

R 2m f n In 2:11 1.

trans QCH COCCH methacrylates, the polymerization will proceed as follows:

R A H \c=c/ H or CH H R A H I polymerization .-c

l H or CH3 H The acrylate and methacrylate monomers are highly reactive and have a great tendency to form both homoor copolymers. The polymer chain with the R, group from the acrylate or methacrylate contains one R; group per monomer moiety. In a homopolymer derived from the novel R, acrylate or methacrylate monomers, the ratio of R; groups to polymer backbone carbon atoms is 1 to 2. If a comonomer is employed the ratio is l to greater than 2, as for example 1 to 4 when 1 mole of R; acrylate or methacrylate is copolymerized with one mole of a comonomer. In the formation of copolymers, the acrylate and methacrylate monomers are highly reactive and form random copolymers.

The polymerization of the R acrylate and R;- methacrylate monomers of type IIa is analogous to the polymerization of acrylate and methacrylate monomers, as described in Houben-Weyl, Methoden der Organischen Chemie, Vol. 14/1, p. 1033-1047, (Georg Thieme Verlag, Stuttgart, 1961) or CE. Schildknecht, Vinyl and Related Polymers, p. 179-255 (John Wiley and Sons, lnc., New York 1952).

in contrast the second group of polymers derived from R fumarates, maleates, mesaconates, citraconates, itaconates and aaconitates show a lower tendency toward homopolymerization and form low-molecular weight homopolymers, also called oligomers. They show however a great tendency to form alternating copolymers with certain types of comonomers as outlined later. In a homopolymer or an alternating copolymer derived from the novel R fumarates and other novel R,-di and triesters, the R,-groups are present in the polymer chain always as either close-packed pairs or triplets of R,-groups and the ratio of R,-groups to polymer backbone carbon is illustratively in a R,-fumarate homopolymer, l to l or I to 2 in an alternating copolymer thereof. The fact that in homopolymers as well as in copolymers of the novel R di and triesters, the R,- groups are always present as close packed pairs or triplets is most important since this close packing yields higher oil repellency ratings.

The following reactions illustrate this closeness of packing of R, groups in the novel diand triesters:

Although the ease of polymerization will differ between the acrylate and methacrylate type monomers on one hand and the fumarate and related monomers on the other, similar conditions may be employed to obtain the desired polymerization.

Generally polymerization may be carried out in bulk, solution, suspension or emulsion. Solution and emulsion polymerizations are preferred.

In emulsion polymerization, the monomer or monomers to be polymerized are emulsified together in a water solution of a surface active agent to a given monomer concentration of from about to about 50 R A AR R A R A I I l C=C Polymerization C-c l l H H (Mdleutel (Polymuleate) R A AR f f t? ef C=C Polymerization C-C l l H R AcH H (Aconitule) In copolymers this closeness of packing of the R, group remains in the fumarate and related monomer moiety.

Of the two classes of polymers derived from the acrylate and methacrylates as opposed to the fumarates and related compounds, certain advantages relate to each group in comparison with the other.

Polymers including alternating copolymers derived from fumarates and related compounds tend to show very low free surface energies and excellent oil repellency ratings due to the fact that closely packed pairs or triplets of R, groups are present in the polymer chain.

R,-fumarates and related diand triester monomers can also be utilized for the synthesis of graft polymers due to the fact that they show a reduced tendency to homopolymerize but an increased tendency toward grafting reactions if compared with the R, acrylates and methacrylates.

In contrast the R,-acrylates and methacrylates contain just one instead of two or more of the heavy R, groups and possess approximately one half to a third of the molecular weight of analogous fumarates and related monomers. Due to the lower molecular weights of the acrylate and methacrylate monomers have a) lower boiling points so that purification via distillation is much easier and b) lower melting points and better so]- ubility properties, a factor most helpful in emulsion polymerization.

Thus it is considered generally from the standpoint of soil repellency the fumarates and related compounds are more highly desirable particularly in forming copolymers but the acrylate and methacrylates do possess good soil repellency qualities in the form of homopolymers and can be desirable for the reasons discussed above.

(Polyclconitutel percent. Usually the temperature is raised to between 40C and C to effect polymerization in the presence of an added catalyst. A suitable catalyst may be any one of the commonly known agents for initiating the polymerization of an ethylenically unsaturated compound. The concentration of the catalyst for the polymerization is usually between 0.1 and 2 percent based upon the weight of the monomers.

Suitable surfactants or emulsifying agents include cationic, anionic or non-ionic types. Since the cationic and non-ionic types can be used in most textile treating baths, they are preferred. The hydrophobic portion of the surfactant may be hydrocarbon or fluorinated hydrocarbon.

Suitable surfactants that may be used include, for example, non-ionic surfactants in which the hydrophilic group is a poly(ethoxy) group and the hydrophobic portion is either a hydrocarbon or a fluorocarbon group such as the ethylene oxide condensates of alkyl phenols, alkanols, alkylamines, alkyl thiols, alkylcarboxylic acids, fluoroalkyl carboxylic acids, fluoroalkyl amides and the like.

Suitable cationic surfactants include for example quaternary ammonium salts or amine salts containing at least one long chain alkyl, fluoroalkyl, or high alkyl substituted benzene or naphthalene group to provide the hydrophobic portion.

Polymerization is preferably carried out for a reaction period adjusted to obtain essentially quantitative conversion of the fluorinated monomer. The optimum reaction time will depend upon the catalyst used and the polymerization temperature and other conditions, but will generally be in the range of from 0.5 to 24 hours.

The polymerization temperature will depend upon the catalyst chosen. In the case of emulsion polymerization in aqueous media, it will generally be in the range of from to 90C. The polymerization is generally most conveniently and preferably carried out at atmospheric pressure wherever possible.

In solution polymerization, the monomer or monomers are dissolved in a suitable solvent such as fluori nated solvents, for example, hexafluoroxylene, trifluorotoluene or mixtures thereof with acetone and/or ethylacetate and polymerized in a reaction vessel using initiators such as azobisisobutyronitrile or other azo initiators at concentrations of 0.1 to 2.0 percent at 40 100C under nitrogen.

As mentioned, besides homopolymers, valuable copolymers are obtained by polymerization of the foregoing novel perfluorinated monomers with other polymerizable monomers having ethylene unsaturation.

The following types of comonomers are useful in the preparation of copolymers of the novel R monomers of type 11:

ethylene and chloro, fluoroand cyanoderivatives of ethylene such as vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride, acrylonitrile, methacrylonitrile, tetrafluoroethylenc. trifluoro-, chloroethylene, hexafluoropropylene; acrylate and methacrylate monomers, particularly those with 1 to 12 or 18 carbon atoms in the ester groups such n-propyl methacrylate, 2-methyl cyclohexyl methacrylate, methyl methacrylate, t-butyl methacrylate, n-butyl methacrylate, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, 3-methyl-l-pentyl acrylate, octyl acrylate, tetradecyl acrylate, s-butyl acrylate, 2- ethylhexyl acrylate, 2-methoxyethyl acrylate, and phenyl acrylate; dienes particularly 1, 3-butadiene, isoprene, and chloroprene, Z-fluoro-butadiene, 1,1,3- trifluorobutadiene, 1,l,2,3-tetrafluoro butadiene, 1,1,- 2-trifluoro-3,4-dichlorobutadiene and triand pentafluoro butadiene and isoprene; nitrogen-vinyl monomers such as vinyl pyridine, N-vinylimides, amides, vinyl succinimide, vinyl pyrrolidone, N-vinyl carbazole and the like;

styrene and related monomers which copolymerize readily with the novel esters of this invention such as vo-methylstyrene, p-methylstyrene, 3,4-dimethyl styrene, 2, 4,6-trimethyl styrene, m-ethyl styrene, 2,5- diethyl styrene;

vinyl esters, e.g., vinyl acetate, vinyl esters of substituted acids, such as for example, vinyl methoxyacetate, vinyl trimethylacetate, vinyl isobutyrate, isopropenyl butyrate, vinyl lactate, vinyl caprylate, vinyl pelargonate, vinyl myristate, vinyl oleate and vinyl linoleate; vinyl esters of aromatic acids, such as vinyl benzoate;

alkyl vinylethers, such as methyl vinyl ether, isopropyl vinyl ether, isobutyl vinyl ether, 2-methoxy ethyl vinyl ether, n-propyl vinyl ether, t-butyl vinyl ether, isoamyl vinyl ether, n-hexyl vinyl ether, 2-ethylbutyl vinyl ether, diisopropylmethyl vinyl ether, l-methyl-heptyl vinyl ether, n-decyl vinyl ether, n-tetradecyl vinyl ether, and n-octadecyl vinyl ether.

Propylene, butylene and isobutylene are preferred a-olefins useful as comonomers with the novel fluoro monomers of the present invention with straight and branched chain a-ole fins useful with up to 18 carbon atoms in the side chain.

Also useful as comonomers with some of the novel monomers of the present invention are vinyl monomers which contain perfluorinated side chains. Examples of such perfluorinated monomers are vinyl ethers of the type disclosed in U.S. Pat. No. 2,732,370 and U.S. Pat.

No. 2,828,025; vinyl esters containing fluorinated alkyl groups disclosed in U.S. Pat. No. 2,592,069 and U.S. Pat. No. 2,436,144. Other useful monomers are acrylates and methacrylates and derivatives thereof such as those disclosed in U.S. Pat. No. 2,628,958; U.S. Pat. No. 3,256,230; U.S. Pat. No. 2,839,513; U.S. Pat. No. 3,282,905; U.S. Pat. No. 3,252,932; and U.S. Pat. No. 3,304,278.

Other R groups containing monomers useful for copolymerization are fumarates, maleates, itaconates, and other a, B-unsaturated diand triesters as described in the co-pending application FCR 27 and the following applications assigned to the assignee of the present invention:

Ser. No. 720,370, filed Apr. 10, 1968, in the names of Eduard K. Kleiner and Martin Knell; Ser. No. 732,040, filed May 27, 1968, in the names of Eduard K. Kleiner, Martin Knell and Pier Luigi Pacini; Ser. No. 812,439, filed Apr. 1, 1969, in the name of Eduard K. Kleiner; Ser. No. 820,647, filed Apr. 30, 1969, in the name of Eduard K. Kleiner; and Ser. No. 833,706, filed June 16, 1969, in the names of Eduard K. Kleiner and Pier Luigi Pacini.

Of the listed comonomers, the acrylate and methacrylate monomers are the most important comonomers for the novel R acrylates and R methacrylates, whereas vinyl ethers, vinyl esters, styrenes and a-olefins are the most important comonomers for the novel R fumarates and related diand triesters due to the fact that they form 1:1 alternating copolymers.

As mentioned, it may also be desirable to include a minor amount of other reactive comonomers in order to improve the wash and dry-clean properties of the novel textile finishes obtained according to the practice of this invention. Such monomers act as cross-linkingagents during the curing operation. Such reactive comonomers are generally employed in amounts of 0.1 to 2 percent.

Reactive monomers which may be included are by way of illustration: acrylic acid, methacrylic acid, acrylamide, methacrylamide, N-methylolacrylamide, 2- hydroxyethyl methacrylate or acrylate, hydroxypropyl acrylates or methacrylates, and t-butylarninoethyl methacrylate, and glycidyl methacrylate. Of the foregoing, N-methylolacrylamide and 2-hydroxyethyl methacrylate are preferred.

Coatings of the homopolymers and copolymers according to the present invention can be prepared and applied from solvent solutions or from aqueous emulsions. Suitable solvents are fluoroalkanes, fluorochloroalkanes, fluoroalkyl substituted aromatics, alkyl esters of perfluoroalkanoic acids, chlorinated alkanes or aromatics, hydrocarbon aromatics, ketones, esters and ethers. Especially useful as solvents are the fluorinated liquids, and especially a,a,a-trifluorotoluene, otherwise known as benzotrifluoride, hexafluoroxylene and mixtures of these with ethyl acetate or acetone and the like. Concentrations of the fluorinated polymers of the present invention in solvent to provide coatings with effective oil and water repellency properties will generally be of the order ofo 0.01 to 10 percent and preferably from 0.1 to 2.0 percent by weight. Blends of the emulsions of the polymers of this invention with blended emulsions of other polymers and copolymers are particularly useful in textile finishes. The polymers and copolymers are generally of a non-fluorinated type; however, as indicated below other fluorinated polymers and copolymers may be used if desired. Nonfluorinated polymers useful in such blends, include for example, but without limitation, polymers and copolymers of alkyl acrylates and alkyl methacrylates, such as methyl methacrylate, ethyl methacrylate, hexyl methacrylate, and n-octyl methacrylate. A particularly suitable polymer is poly-n-octyl methacrylate. Also useful are polymers and copolymers of acrylic acid, methacrylic acid, styrene, alkyl styrene, butadiene, Z-methyI'IfB-butadiene, 2'chloro-1,3-butadiene; polymers and copolymers of vinyl esters such as vinyl acetate, vinyl butyrate, vinyl laurate, vinyl stearate, vinyl 2- ethyl-hexanoate; polymers and copolymers of vinyl halides and vinylidene halides, such as vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride; polymers and copolymers of allyl esters such as allyl propionate, or allyl caprylate; polymers and copolymers of vinyl ketones, such as vinyl methyl ketone, vinyl ethyl ketone, and the like; polymers and copolymers of vinyl ethers such as methyl vinyl ether, cetyl vinyl ether, and the like; polymers and copolymers of acrylamide, methacrylamide, N-methylol acrylamide, N-methylol methacrylamide, N-isopropyl acrylamide, and acrylonitrile and methacrylonitrile.

The polymers of this disclosure possess desirable soil EXAMPLE 4 9 As outlined in Table l, mercaptans of the type (CF CFO(CF CF CH CH SH are added to vinyl acetate employing conditions and catalyst as described in Example la of copending Parent application, Ser. No. 199,793. The resulting acetates of the type (CF9 CFO(CF CF CI-I CH SCH CH OOCCH can be used directly for the synthesis of R thioether monomers of type II employing transesterification techniques. Hydrolysis of the novel acetates yields R,- thioether alcohols of the type (CF CFO(CF CF ),,CH CH SCH CH OH.

TABLE 1 R mercaptans R iodides and mercaptans R thioether alcohols repellency properties. A useful manner of measuring the relative ratings of the polymers is by oil and water repellency ratings. In the examples the following test procedures were used:

The AATCC Oil Rating was determined according to Standard Test Method 118-1966 T of the American Association of Textile Chemists and Colorists. Ratings are given from 0 (minimum) to 8 (maximum). A commonly accepted level on soil repellency fabrics in the US. is an oil repellency of 4.

Another oil repellency method is the 3-M Oil Test procedure of Grajek and Peterson, Textile Research Journal, April 1962, p. 323.

The AATCC water spray test rating was determined according to Standard Test method 22-1966 of the American Association of Textile Chemists and Colorists XXXVII, 1961 p. 1952 (also designated ASTM-D- 583-58). Ratings are given from 0 (minimum) to 100 (maximum).

The polymers in the examples were applied to polyester or polyester-cotton (65 percent/ percent). The polymers were applied to yield a concentration of 0.08 and 0.12 percent fluorine based on the weight of the fabric.

To further illustrate the novel aspects of this invention relating to the novel thioether alcohols of type I, the a, B-unsaturated mono, diand triesters of type II, and the polymers of type III, the following examples are provided:

EXAMPLES 1 3 Ry-tlllthf alcohols of the type (CF CFO(CF CF ),,CH CH SCH -CH CH OI-I, wherein n 1, 2 or 3 EXAMPLE 10 Bis( 6-perfluorooctyl-4-thiahex- 1 -yl) fumarate,

CHCOOCH CH CH SCH CH C F 2 nances at 62.02, 4 protons in a multiplet, 2X(COOCH :fl CH 522-30, 12 protons in overlapping multiplets, 2X(COOCH CH C H S) and 2X(SCH CH- CF 84.33, 4 protons in a triplet, 2X(COOQfl CH 86.85, 2 protons in a singlet, C H=C I' I. These data are consistent with the above structure.

Analysis for O l-1 5 0 8 Cale: C, 31.15; H, 1.92; F, 55.85 Found: C, 3133; H, 1.96; F, 56.86

EXAMPLE 1 1 6-Perfluorooctyl-4-thiahexan-1-1 (200g, 0.0372 mole, example 1), spectrograde toluene (g) and itaconyl chloride (3.11g, 0.0186 mole, distilled) were refluxed, for 22 hours at which time a VPC analysis showed complete reaction. The toluene was evaporated from the reaction mixture and the residue was redissolved in chloroform and then was passed through a column of aluminum oxide (neutral activity I). The

showed a complete reaction. The reaction mixture was cooled and the solvent was stripped off in a rotary film evaporator. The residue was crystallized 2 times from hexane yielding 124;; of white flakes with an mp product was worked from the column with 500 ml of 5 51-52C (72 percent yield). The NMR showed proton chloroform which was then stripped off inarotary film resonances at 82.05, 4 protons in a multiplet, evaporator. The solid residue was crystallized from ZX(COOCH Qfl CH S; 5115-31) 8 protcns i Overhexane and 6.8g of white crystals were obtained (mp lapping multiplets, 2X(COOCH CH QH S Cfl CF 6869C, 31 percent yield). The NMR showed proton 84.32, 4 protons in a triplet, 2X(COOQfl CI-I CH- resonances at 8165-24, 4 protons in multiplets, 10 S--); 86.85, 2 protons in a singlet, (lfli. These 2X(COOCH (J CH S); 823-30 12 protons in comdata are consistent for the above structure. plex overlapping multiplets, 2X(CH C l1 S( Ifl Ql l CF 83.32, 2 protons in a singlet,C(COO)@ COO;84.l-4.5,4 protons in over- A I v f C H F lapping triplets COOCH2QlI-2 and 15 ysls or 26 22 2 iiale; c, 32.64; H. 2.32; ,51.64 CH COOQfl CH 85.71 and 86.32, 2 protons in sin- Found: 52-10 glets EXAMPLE 13 l6 Ql l =C Monomers of type 11 derived from 6-Perfluoroalkyl-4-thiahexanl -OL Employing a transesterification procedure (as described in Example 17 of copending Parent application These data are consistent with the above structure. 25 Ser. No 199,793 fumarates, maleates, itaconates and trans-aconitates were prepared from 6-perfluoroalkyl- 4-thiahexan-l-ol (preparation may be found in exam- Analysis for C.,,H .,F ,O.,s 8 S 8 ple 3 of parent application Ser. No. 199,793) and the C l C, 31.80; H, 2.07; F, 55.1 5,4 12 d: C, 3194; H, 209; F, 5490; S 679 methyl esters of acrylic methacrylic, fumaric, malelc,

itacomc and trans-aconitic acid as shown in table 2.

TABLE;

Example R -thiuether alcohols- 11.: red 'ofTypcll No. of type I esters 13 Z t=CHCO0CH .trans (CHCO0CH CH SCH CH R I .trans l4 2 (=CHCO0CH .cis 1=CHCOOCH CH CH SCH CH R .sis

l5 2 'CH2=C(COOCH3)CHZCOOCH3 CH =CICOOCH CH CH SCH CH RflCH COOCH CH CH SCH CH R l6 3 n cooc C C coocn R cH cn srcu 00c\C C coo(Cn 1 sCn cn R n c0occu H R,cn cn slcn l ooccn \H EXAMPLE l2 EXAMPLES 17-20 Bis(6- erfluorohexyl-4-thiahex-l-yl) fumarate,

=CgcoocH2CH2 CH2SCH2CH2C6F13]2 Monomers of type 11 derived from R -thioether acetates 6-Perfluorohexyl-4-thiahexan-1- g. 0036 Employing a transesterification procedure, monomole, example 2), spectrograde toluene (g) and fumaryl chloride (2.75g, 0.018 mole, distilled) were refluxed for 20 hours at which time a VPC analysis ABL 3 Example R -thiuether acetates Esters Prepared as in Example 13 ol'Parcnt Application Ser. No. 199.793

Prepared as in Example 14 of Parent Application Ser. No. 199.793

mers of type II as listed in Table 3 were prepared from the listed R -thioether acetates and the methyl esters of fumaric, maleic and itaconic acid.

a.,$-nns:1turatcd Monomers of Type 11 2(CF 1 0-01 cr cr ut ca scn cn oocca HJHCOOL'H3 1 mm 9 -cncoocn 0H scn CHzlCF L'FgbOCFlCE; l 1

EXAMPLES 21 30 Ten parts of monomer mixtures of equimolar amounts of novel R fumarate or itaconate monomers and comonomers as listed in Table 6, 0.05 parts of am- EXAMPLES 32 34 Polymers example 22, 25 and 27 were dissolved in hexafluoroxylene or freon l 13 and polymer films preblsisobutyromtrile and parts of hexafluoroxylene pared b placmg a f drops f h polymer l n were Sealed in an ampul under nitrogen and p y on a glass slide and with a clean edge spreading the soiZed for 16 hours at The resulting P y Solulution over the surface of the slide. Instantaneous soltions were diluted with 30 parts of hexafluoroxylene vent tio l ft the olymer as a smooth film. and added dropwlse into 800 Parts of methanol under 10 Contact angles of octane to tetradecane on the polymer vigorous stirring. The prec pitated polymers were films were measured using a Visco-Tech contact antle separated by filtration from the sol ent-no so e t analyzer. From the contact angle data the critical surmixture and dried under high-vacuum at room temperface tension 7 0 was determined according to the folature for 48 hours. Yields, appearance and fluorine l wing reference: analysis of the novel copolymers are listed in Table 4. W. Zisman, Contact Angles, Advances in Chemistry,

TABLE 4 Example Composition of Monomer Mixture Appearance Yield Elemental Analysis No. Equimolar Ratio of R monomer to Comonomcr) of after Calc.

C opolymer ppt. Found C H F R Monomer Comonomer 2l Fumarate of CH =CHO(CH OH White Culc. 33.97 2.69 50.76 C,,F (CH S(CH );,OH Hydroxybutyl Soft 884% Found 33.73 2.49 50.40

Ex. 10 Vinyl Ether Polymer 22 as above CH=CHOCH; White Cole. 3268 2.33 5 .l 1 Methyl Vinyl Powder 905% Found 32.70 2.26 .21 Ether 23 as above CH =CHC H White Cale. 36.20 2.40 51.02 Styrene Powder 86.3% Found 36.28 2.66 53.02 24 ltaconate of CH =CHO(CH OH White Cale. 34.53 2.82 50.20 C F, (CH S(CH OH Hydroxybutyl Soft 87.3% Found 33.53 2.58 5 l .72

Ex. ll Vinyl Ether Polymer 25 as above CH =CHOCH White Cale. 33.23 2.46 52.58 Methyl Vinyl Powder 900% Found 32.27 2.29 54.04 Ether 26 as above CH =CHC H White Calc. 36.74 2.53 50.68 Styrene Powder 89.05% Found 36.95 2.78 52.86 27 Fumarate of CH =CHOCH;, White Cale. 34.33 2.78 48.69 C F, (CH S(CH );,OH. Methyl Vinyl Soft 99.4% Found 34.28 2.62 49.69

Ex. l2 Ether Polymer 28 as above CH =CHO(CH OH White Calc. 35.83 3.19 46.05 Hydroxybutyl Soft 77.6% Found 35.23 2.99 49.12 Vinyl Ether Polymer 29 as above CH =CHC H White Cale. 38.50 2.85 46.57 Styrene Soft 76.4% Found 39.42 3.0] 48.55

Polymer 30 as above CH =CHOCOCH White Calc. 34.56 2.71 47.38 Vinyl acetate Soft 77.5% Found 34.0l 2.60 5l.60

Polymer EXAMPLE 3] No. 43, ACS Publications, Washington, DC, 1964.

The critical surface tension data obtained with the 3 Employing the polymerization procedure described polymers are listed in Table 5.

TABLE 5 Examp Polym Polymer Composition Molar Monomer 7 c N0. EX. Ratio of ldynes/cm) R Monomer Comonomer R Monomer to Comonomer 32 37 l=CHCOO(CH S(CH 2 CH =CHOCH lzl ll.5

CH =CCOO(CH S(Cl-l C F 33 40 I CH =CHOCH lzl ll.2

CH CO0(CH S(CH C F 2 3 34 42 (=CHCOO(CH S(CH C F CH =CHOCH l:l l3.l

for examples 21 to 30, alternating copolymers of the novel R monomers examples l3 through 20 and the EXAMPLES 35 42 following comonomers are prepared:

methyl vinyl ether ethyl vinyl ether butyl vinyl ether 4-hydroxybutyl vinyl ether Z-methoxyethyl vinyl ether vinyl acetate vinyl benzoate Homoand copolymers examples 21, 22, 24, 25, 27,

28, 29, and 30 were dissolved in hexafluoroxylene so that solutions with a 2 percent solid content were obtained. These polymer solutions were further diluted with methyl chloroform and applied alone or in combination with a polymethyl methacrylate extender to a polyester fabric by padding in such a way that 0.12 percent fluorine was deposited onto the test fabric. After sytrene p-chlorostyrene p-methoxystyrene isobutylene drying the fabric at 150C for 3 minutes oil repellencies (AATCC and 3 M oil test) and water repellencies were determined and data obtained as listed in Table 6.

misZto l2, nis3to 12,

Example Polymer Polym r Composition Mum Ratio Repellency with 0.129 Fluorine on PE El -Monomer Comouomcr of RrMolwmer xxrcc/s M Oil AATCC Water to Colnonomer l I No Extender Extended i No Extender Extender i 35 21 |=CHCtCl-l StCH C F 2 cu em/01 1 011 1:1 0 120 0-1/110 00100 90 100 36 22 as above CH2=CHOCH3 ltl 5 6/100 5/90 90-| 00 100 CH=CCOO(CH J S(CH C F 37 24 I CH =CHOiCH CH lIl 2 100 CHZCOOCHZBSCHZZCSFW Z 1 6 7 1 0 0 7,120 100 38 nsabove c14 =c11oc11 1:1 50 100 0/100 90 100 39 27 I=CHCOO(CHZ)ZSICHZ)ZC6FI 3| 2 CH2=CH0(CH2)4OH 1:1 5 100 50 110 90 00 40 2x as above cu =c11ococ14 1:1 5 00 5 90 90 00-100 41 20 asabove cn =cnc n 111 4/80 4/80 90 90 100 42 so as above at =cnocn 3 111 4 00 4 00 70 110 The fluoropolymers are extended with polymethyl methucrylate to a F-coutent of 2071 in total solids.

EXAMPLES 43 48 p is 3 to 18, and

. i 2 to 8. Home and copolymers of examples 21 26 were dlS' 2 The com ound of claim 1 wherein m is 2 or 3 and solved as described in the previous examples and ap 30 n 3 p plied above or in combination with a polyisobutyl of cla1m 2 wherein 1s 6 to 12. methacrylate extender to a polyester-cotton test fabrtc El Compoung f l 2 h in such a way that in each case a total of 0.08 percent e compoun 0 C f W erem m 2m 15 fluorine was deposited onto the test fabric. After drying The compound of claim 4 wherejm equals "r the treated fabric at 150C for 3 minutes, AATCC and The compound of Glam 3 wherem m 15 2 or 3 and 3 M oil repellency and AATCC water repellency ratn is 3. ings were determined as listed in Table 7. 7. The compound of claim 4 wherein n is 3 to 6.

TABLE 1 Example Polymer Polymer Composition Molar Ram, Repellency with 0.08% fluorine on PE Cotton R M nomer Comonomer of R Monomer AATCCB M on AATCC water 0 No Extender Extended No Extender Extended H 43 21 |=CHCOOtCH S(CH C F 2 c|1 =c11o cn 1:1 4/80 5/00 80-90 80 44 22 as above c11 =c11oc11 111 4/00 4-5 90 70-80 10 30 45 23 as above CH 2=CHC6H5 1:1 4 00 5 00 00 00-90 46 24 c1:?COOCHZJ3SCHZ)ZCgFl7 cu 2=CHO1CH 7 1 01 1:1 5/90 5/90 80 so CH2CO0(CH2)3SICHZ)2C6F]7 47 Z5 33 qbuve CHZ=CHOCH3 111 5/90 6/100 80 90 4s 20 as above c11 =c11c 11 111 4/80 5 90 8000 80-90 The l'lnorupolymers are extended with pulyisobutyl lnethucrylntc to n F-content of 20% in total solids wherein 8. The compound of claim 7 wherein C l'l is linear and m equals n.

UNITED STATES PATENT AND TRADEMARK OFFICE CERTIFICATE OF CORRECTION PATENT NO. 3,884,879 DATED May 20, 1975 INVENTOMS) 1 Eduard Karl Kleiner It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

Claim 1, column 18, line 3, "F should read En'gncd and Scaled this fourteenth Day of October 1975 [SEAL] Attest.

RUTH C. MASON C. MARSHALL DANN ff Commissioner ofParents and Trademarks 

1. A COMPOUND OF THE FORMULA: RFCMH2MSCNH2NOH WHEREIN M IS 2 TO 12, N IS 3 TO 12, RF IS CPF2P+1OCQF24 P IS 3 TO 18, AND Q IS 2 TO
 8. 2. The compound of claim 1 wherein m is 2 or 3 and n is
 3. 3. The compound of claim 2 wherein p is 6 to
 12. 4. The compound of claim 2 wherein CmH2m is linear.
 5. The compound of claim 4 wherein m equals n.
 6. The compound of claim 3 wherein m is 2 or 3 and n is
 3. 7. The compound of claim 4 wherein n is 3 to
 6. 8. The compound of claim 7 wherein CmH2m is linear and m equals n. 